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US9315655B2 - Fiber reinforced resin molding compound and manufacturing method for fiber reinforced resin molded article therefrom - Google Patents

Fiber reinforced resin molding compound and manufacturing method for fiber reinforced resin molded article therefrom Download PDF

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US9315655B2
US9315655B2 US14/363,332 US201214363332A US9315655B2 US 9315655 B2 US9315655 B2 US 9315655B2 US 201214363332 A US201214363332 A US 201214363332A US 9315655 B2 US9315655 B2 US 9315655B2
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curing agent
resin
microencapsulated
microencapsulated curing
smc
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US20140329962A1 (en
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Mitsuru Akagawa
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Owens Corning Intellectual Capital LLC
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OCV Intellectual Capital LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/241—Preventing premature crosslinking by physical separation of components, e.g. encapsulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/243—Two or more independent types of crosslinking for one or more polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/06—Unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients

Definitions

  • the general inventive concepts relate to fiber reinforced resin molding compounds and methods of manufacturing fiber reinforced resin molded articles therefrom.
  • Sheet molding compounds (“SMC”), bulk molding compounds (“BMC”), and thick molding compounds (“TMC”) are fiber reinforced thermosetting resin molding compositions (sometimes referred to hereinafter as “compounds” in accordance with customary practice in this field) which are widely used in industrial molding processes such as compression molding, etc.
  • Such fiber reinforced thermosetting resin molding compounds typically comprise a curable polymer resin and a curing agent capable of causing the resin to cure when the molding compound is heated or otherwise processed to activate the curing agent.
  • These conventional compounds encounter problems when used for molding articles having a thickness of 5 mm or more. The problems can include, for example, relatively long curing times, insufficient curing, and/or poor appearance of the resulting molded article. Accordingly, there is a need for fiber reinforced resin molding compounds that overcome or mitigate one or more of these problems, and/or any other problems, of the conventional compounds.
  • the general inventive concepts relate to and contemplate reinforced resin molding compounds and methods of manufacturing fiber reinforced resin molded articles therefrom.
  • the general inventive concepts are applicable to fiber reinforced resin molding compounds, such as SMC, BMC, TMC, etc.
  • a molding compound comprising a resin composition and reinforcing fibers.
  • the resin composition contains an unsaturated polyester resin, a microencapsulated curing agent, and a non-microencapsulated curing agent.
  • the microencapsulated curing agent is a thermal responsive microencapsulated curing agent.
  • the non-microencapsulated curing agent has a lower activity compared with the microencapsulated curing agent.
  • the microencapsulated curing agent contains an organic peroxide having a one minute half-life temperature of 115° C. to 140° C.
  • the non-microencapsulated curing agent contains an organic peroxide having a one minute half-life temperature of 130° C. to 170° C.
  • the microencapsulated curing agent contains an organic peroxide having a one minute half-life temperature of 120° C. to 130° C.
  • the non-microencapsulated curing agent contains an organic peroxide having a one minute half-life temperature of 140° C. to 160° C.
  • the resin composition contains the microencapsulated curing agent and the non-microencapsulated curing agent in the ratio of from 0.5 to 5 parts per hundred parts resin by weight as the net amount of sum of all organic peroxides.
  • the resin composition contains the microencapsulated curing agent and the non-microencapsulated curing agent in the ratio of from 0.2 to 2 parts by weight to 1 part by weight, respectively, as the net amount of organic peroxide contained in each curing agent.
  • the resin composition further contains at least one additive selected from the group consisting of a low-shrinkage agent, a filler, a thickener, an anti-crack agent, an anti-separation agent, a mold release agent, and an inhibitor.
  • a manufacturing method for a fiber reinforced resin molded article comprises molding a molding compound by compression molding, wherein the molding compound comprises a resin composition and reinforcing fibers.
  • the resin composition contains an unsaturated polyester resin, a microencapsulated curing agent, and a non-microencapsulated curing agent.
  • the microencapsulated curing agent of the molding compound used in the manufacturing method is a thermal responsive microencapsulated curing agent.
  • the non-microencapsulated curing agent of the molding compound used in the manufacturing method has a lower activity compared with the microencapsulated curing agent.
  • the microencapsulated curing agent contains an organic peroxide having a one minute half-life temperature of 115° C. to 140° C.
  • the non-microencapsulated curing agent contains an organic peroxide having a one minute half-life temperature of 130° C. to 170° C.
  • the microencapsulated curing agent contains an organic peroxide having a one minute half-life temperature of 120° C. to 130° C.
  • the non-microencapsulated curing agent contains an organic peroxide having a one minute half-life temperature of 140° C. to 160° C.
  • the resin composition of the molding compound used in the manufacturing method contains the microencapsulated curing agent and the non-microencapsulated curing agent in the ratio of from 0.5 to 5 parts per hundred parts resin by weight as the net amount of sum of all organic peroxides.
  • the resin composition of the molding compound used in the manufacturing method contains the microencapsulated curing agent and the non-micro encapsulated curing agent in the ratio of from 0.2 to 2 parts by weight to 1 part by weight, respectively, as the net amount of organic peroxide contained in each curing agent.
  • the resin composition of the molding compound used in the manufacturing method further contains at least one additive selected from the group consisting of a low-shrinkage agent, a filler, a thickener, an anti-crack agent, an anti-separation agent, a mold release agent, and an inhibitor.
  • the fiber reinforced resin molding compounds can exhibit a shelf life sufficient for practical use of the compounds after a reasonable storage period thereof.
  • the fiber reinforced resin molding compounds can retain flowability during the molding process such that the appearance of the resulting molded article is good.
  • the fiber reinforced resin molding compounds can be cured rapidly during the molding process, such that the overall molding time is shortened.
  • the fiber reinforced resin molding compounds can exhibit a high degree of cure, even for molded articles having a thickness in excess of 5 mm.
  • the general inventive concepts relate to and contemplate fiber reinforced resin molding compounds and methods of manufacturing fiber reinforced resin molded articles therefrom. While the general inventive concepts are susceptible of embodiment in many different forms, there are described herein in detail specific embodiments thereof with the understanding that the present disclosure is to be considered as an exemplification of the principles of the general inventive concepts. Accordingly, the general inventive concepts are not intended to be limited to the specific embodiments described herein.
  • a molding compound for manufacturing a fiber reinforced molded article comprises a resin composition and reinforcing fibers.
  • the resin composition contains an unsaturated polyester resin, a microencapsulated curing agent and a non-microencapsulated curing agent.
  • the resin composition contains the microencapsulated curing agent and the non-microencapsulated curing agent in the ratio of from 0.5 to 5 PHR (parts per hundred parts resin by weight) as the net amount of sum of all organic peroxides.
  • the resin composition contains the microencapsulated curing agent and the non-microencapsulated curing agent in the ratio of from 0.2 to 2 parts by weight to 1 part by weight, respectively, as the net amount of organic peroxide contained in each curing agent.
  • microencapsulated curing agent providing the desired properties described herein can be used.
  • the microencapsulated curing agents described in the pending U.S. patent application having Ser. No. 13/436,161 and filed on Mar. 30, 2012 published as U.S. 2012/0248639 on Oct. 4, 2012, the entire disclosure of which is incorporated herein by reference, can be used in this invention.
  • suitable curing agents can include, for example, dilauroyl peroxide, t-butyl peroxy-2-ethylhexanoate, 1,1,3,3-tetramethyl butylperoxy-2-ethylhexanoate, t-amyl-2-peroxy-2-ethylhexanoate and dibenzoyl peroxide.
  • the microencapsulated curing agents may be made by any known encapsulation technique.
  • the encapsulation techniques provided by Lyco Technologies, Inc. may suffice in forming the microencapsulated curing agents.
  • Interfacial polymerization is a process wherein a microcapsule wall of a polymer resin such as a polyamide, an epoxy resin, a polyurethane resin, a polyurea resin or the like is formed at an interface between two phases.
  • the basic approach of the interfacial polymerization process is to (a) dissolve the peroxide curing agent and the isocyanate forming the polyurethane in an organic solvent which is essentially immiscible with water and a non-solvent for the polyol and optional polyamine forming the polyurethane, (b) emulsify the organic solution so formed in an aqueous phase by vigorous mixing, and then (c) add the polyol and optional polyamine to the emulsion so formed with continuous mixing to cause the polyurethane to form at the interface of the emulsified particles.
  • Forming microcapsules by interfacial polymerization is well-known and described in a number of publications. For example, such techniques are described in Masumi, et al., CREATION AND USE OF MICROCAPSULES, “1-3 Manufacturing Method and Use of Microcapsules,” Page 12-15, ⁇ 2005 by Kogyo Chosa Kai K.K. (ISBN4-7693-4194-6 C3058). Such techniques are also described in Mitsuyuki et al., APPLICATION AND DEVELOPMENT OF MICRO/NANO SYSTEM CAPSULE AND FINE PARTICLES, “4-3 Manufacturing method of Thermal Responsive Microcapsules,” Page 95-96, 2003 by K.K. CMC Shuppan (ISBN978-4-7813-0047-4 C3043).
  • a thermal responsive microencapsulated curing agent is preferably used as the microencapsulated curing agent.
  • the thermal responsive microencapsulated curing agent is heated to a specific temperature that is required to practice a heat-press molding method, organic peroxide contained therein is emitted from the microcapsule.
  • the microencapsulated curing agent desirably contains organic peroxide having a one minute half-life temperature of 115° C. to 140° C., and more desirably 120° C. to 130° C.
  • organic peroxide having a one minute half-life temperature of 115° C. to 140° C., and more desirably 120° C. to 130° C.
  • non-microencapsulated curing agent providing the desired properties described herein can be used.
  • the non-microencapsulated curing agent can be a curing agent that is normally used for a conventional fiber reinforced resin molding compound, such as SMC.
  • the non-microencapsulated curing agent can be a liquid, powder or particle.
  • the non-microencapsulated curing agent has a lower activity compared with the microencapsulated curing agent. As a result, a problem of a shortened shelf life of the molding compound is prevented.
  • the non-microencapsulated curing agent desirably contains organic peroxide having a one minute half-life temperature of 130° C. to 170° C., and more desirably 140° C. to 160° C.
  • 1,1-di(t-hexylperoxy)cyclohexane one minute half-life temperature: 149° C.
  • t-Amyl peroxy isopropyl carbonate one minute half-life temperature: 153° C.
  • t-butyl peroxy isopropyl monocarbonate one minute half-life temperature: 159° C.
  • t-butyl peroxy benzoate one minute half-life temperature: 169° C.
  • a mixture of at least two organic peroxides selected from above can, for example, be used.
  • microencapsulated curing agent By combining the microencapsulated curing agent and the non-microencapsulated curing agent, sufficient activity of the curing agents is obtained, and flowability of the molding compound can be retained during the molding process. As a result, even in a case where a molding time of a thick molded article is short, a sufficient degree of cure can be obtained, and the appearance of the resulting molded article is good.
  • the total amount of the microencapsulated curing agent and the non-microencapsulated curing agent contained in the unsaturated polyester resin composition should be sufficient, so that the net amount of sum of all organic peroxides present is about 0.5 to 5 PHR, more typically 0.8 to 4 PHR, or even 0.9 to 3 PHR.
  • PHR means “parts per hundred parts resin by weight,” namely a ratio of the additive to the resin ingredients of 100 parts by weight. In this unit, the resin ingredients are the sum of the unsaturated polyester resin and the low shrinkage additive.
  • the ratio of the microencapsulated curing agent to the non-microencapsulated curing agent preferably is 0.2 to 2 parts by weight to 1 part by weight, and more preferably is 0.3 to 1.5 parts by weight to 1 part by weight. This ratio is expressed by the net amount of organic peroxide contained in each curing agent.
  • the molding compound for manufacturing a fiber reinforced molded article comprises a resin composition and reinforcing fibers.
  • the resin composition contains an unsaturated polyester resin, the above mentioned microencapsulated curing agent, and the non-microencapsulated curing agent.
  • the resin composition can further contain at least one additive selected from the group consisting of a low-shrinkage agent, a filler, a thickener, an anti-crack agent, an anti-separation agent, a mold release agent, and an inhibitor.
  • the unsaturated polyester resin and/or these additives can be the same as the resins and additives that are used in conventional molding compounds such as SMC.
  • the reinforcing fibers are glass fibers.
  • the glass fibers have a filament diameter of 5-20 ⁇ m.
  • Such glass fibers can be continuous or chopped, and if chopped desirably have a length of 20-100 mm.
  • such filaments can also be formed into strands.
  • the reinforcing fibers are strands having a yarn count (weight per unit length) of 50-5,000 gm/km.
  • the reinforcing fibers are strands having a bundling number of 50-200 filaments per strand.
  • such glass fibers, and/or the strands and yarns made therefrom can be coated with a suitable sizing agent containing a silane coupling agent, the sizing agent also optionally containing a film-forming agent such as a polyurethane or polyvinyl acetate resin, and other conventional ingredients such as cationic and nonionic surfactants and the like.
  • the reinforcing fibers are non-glass fibers, such as carbon fibers.
  • any amount of the reinforcing fibers can be included in the thermosetting resin molding compounds.
  • the molding compounds of the general inventive concepts can have a form such as sheet molding compounds (“SMC”), bulk molding compounds (“BMC”), or thick molding compounds (“TMC”).
  • SMC sheet molding compounds
  • BMC bulk molding compounds
  • TMC thick molding compounds
  • a manufacturing method for a fiber-reinforced resin molded article involves these molding compounds being molded to obtain the molded article, such as by a compression molding method.
  • Tables 1 and 2 illustrate various working examples of molding compounds that comport with the general inventive concepts described herein.
  • resin compositions having formulations described in Table 2 were prepared, and curing agents mentioned in Table 1 were used in these compositions.
  • Table 3 relates to evaluating the samples for shelf life.
  • the resin compositions were individually put in steel can with a cap, and they were aged under atmosphere at a temperature of 40° C. over two days. Then, they were kept under room temperature. After a specific amount of time had passed, the condition of each resin composition was visually inspected and evaluated by criteria noted in Table 3. The results obtained are set forth in the following Table 3.
  • the exemplary molding compounds of the general inventive concepts have sufficient shelf life as lengthy as a conventional molding compound using Resin Composition-Y, because inventive Resin Composition-1 has sufficient flowability even after 101 days passed. Furthermore, it is understood that the shelf life of the molding compounds using Resin Composition-V or Resin Composition-Z, which contain a non-microencapsulated curing agent with high activity, is so short as to be impractical.
  • Table 4 relates to evaluating the samples for moldability (curing speed) in the context of a SMC.
  • Resin Composition-1 was formulated into a sheet molding compound (SMC-1) by combining 66 wt. % of a chopped glass fiber strand having a length of about 25 mm, the chopped glass fiber strand being made from a glass fiber strand having a linear density of 75 gm/km, a bundling number of 150 filaments per strand and a filament diameter of 16 ⁇ m, the glass fiber strand being sized with 0.95 wt. % of a sizing agent containing a silane coupling agent, a polyurethane resin and a polyvinyl acetate resin.
  • SMC-1 sheet molding compound
  • Resin Composition-V to Resin Composition-Z were formulated into a sheet molding compound (SMC-V to SMC-Z) by combining 66 wt. % of each molding resin with 34 wt. % of the same chopped glass fiber strand used to make sheet molding compound SMC-1.
  • Each of the sheet molding compounds so made was then molded into a flat plate having a thickness of 3 mm or 5 mm by means of a heat-press molding machine in which an upper platen heated to a temperature of 140° C. and a lower platen heated to 145° C. were compressed together at a cylinder pressure of 180 kg/cm 2 . After a specific amount of time under these conditions, the platens were opened, and the molded plates were visually inspected for surface appearance and condition of cure. Then, according to the criteria noted in Table 4, surface appearance and condition of cure were evaluated. The results obtained are set forth in the following Table 4.
  • SMC-Y which is a conventional SMC.
  • SMC-1 as an exemplary inventive SMC was cured sufficiently in a time shorter than this standard molding time, such as 90, 70, and 60 seconds. This evidences a more rapid cure of SMC.
  • SMC-V namely SMC containing the microencapsulated curing agent and the non-microencapsulated curing agent, both having high activity, its cure condition was poor.
  • Table 5 relates to evaluating the SMC samples for cure time.
  • Cure Time of SMC was measured by the method using the equipment having the name of “Cure Tool.” Test conditions and the results obtained are set forth in the following Table 5.
  • Cure Time means the required time until reaching the highest temperature from start of heating.
  • the Cure Time of SMC-1, SMC-2 and SMC-3, as inventive SMCs are shorter than SMC-Y, as a conventional SMC.
  • Table 6 relates to evaluating the SMC samples for specular glossiness.
  • specular glossiness of molded articles made from the above-mentioned SMCs was measured by the method according to JIS Z8741, on an incident angle of 60 degrees. The results obtained are set forth in the following Table 6.
  • a conventional SMC namely SMC-Y
  • the glossiness of its molded article tends to decline with shortening of compressing time.
  • all of the molded articles made from SMC-1, as an inventive SMC have glossiness equivalent to the molded article made from conventional SMC by the standard molding time.
  • Tables 7 and 8 relate to evaluating the SMC samples for bending strength and bending modulus, respectively.
  • bending strength and bending modulus of molded articles made from SMC-1 and SMC-4, as exemplary inventive SMC, and SMC-Y, as a conventional SMC were measured. Test conditions and the results obtained are set forth in the following Table 7 and Table 8.
  • inventive fiber reinforced resin molding compounds have been shown to provide superior properties over those presented by conventional fiber reinforced resin molding compounds.
  • SMC-1 as an exemplary inventive molding compound, obtained excellent results in both shelf life and curing condition.
  • the general inventive concepts further contemplate manufacturing methods for producing fiber reinforced resin molded articles, the manufacturing methods using any of the fiber reinforced resin molding compounds described or suggested herein.

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Abstract

A molding compound for manufacturing a fiber reinforced molded article is provided. The molding compound includes a resin composition and reinforcing fibers, with the resin composition containing an unsaturated polyester resin, a microencapsulated curing agent and a non-microencapsulated curing agent.

Description

RELATED APPLICATIONS
The present application is the U.S. national phase entry of PCT/US12/68132, filed on Dec. 5, 2012 which claims priority/benefit of the U.S. provisional patent application having Ser. No. 61/568,485 and filed on Dec. 8, 2011, and the U.S. provisional patent application having Ser. No. 61/596,326 and filed on Feb. 8, 2012, the entire disclosures of which are fully incorporated herein by reference.
FIELD
The general inventive concepts relate to fiber reinforced resin molding compounds and methods of manufacturing fiber reinforced resin molded articles therefrom.
BACKGROUND
Sheet molding compounds (“SMC”), bulk molding compounds (“BMC”), and thick molding compounds (“TMC”) are fiber reinforced thermosetting resin molding compositions (sometimes referred to hereinafter as “compounds” in accordance with customary practice in this field) which are widely used in industrial molding processes such as compression molding, etc. Such fiber reinforced thermosetting resin molding compounds typically comprise a curable polymer resin and a curing agent capable of causing the resin to cure when the molding compound is heated or otherwise processed to activate the curing agent. These conventional compounds, however, encounter problems when used for molding articles having a thickness of 5 mm or more. The problems can include, for example, relatively long curing times, insufficient curing, and/or poor appearance of the resulting molded article. Accordingly, there is a need for fiber reinforced resin molding compounds that overcome or mitigate one or more of these problems, and/or any other problems, of the conventional compounds.
SUMMARY
The general inventive concepts relate to and contemplate reinforced resin molding compounds and methods of manufacturing fiber reinforced resin molded articles therefrom.
The general inventive concepts are applicable to fiber reinforced resin molding compounds, such as SMC, BMC, TMC, etc.
In one exemplary embodiment of the general inventive concepts, a molding compound comprising a resin composition and reinforcing fibers is provided. The resin composition contains an unsaturated polyester resin, a microencapsulated curing agent, and a non-microencapsulated curing agent.
In one exemplary embodiment of the general inventive concepts, the microencapsulated curing agent is a thermal responsive microencapsulated curing agent.
In one exemplary embodiment of the general inventive concepts, the non-microencapsulated curing agent has a lower activity compared with the microencapsulated curing agent.
In one exemplary embodiment of the general inventive concepts, the microencapsulated curing agent contains an organic peroxide having a one minute half-life temperature of 115° C. to 140° C., and the non-microencapsulated curing agent contains an organic peroxide having a one minute half-life temperature of 130° C. to 170° C.
In one exemplary embodiment of the general inventive concepts, the microencapsulated curing agent contains an organic peroxide having a one minute half-life temperature of 120° C. to 130° C., and the non-microencapsulated curing agent contains an organic peroxide having a one minute half-life temperature of 140° C. to 160° C.
In one exemplary embodiment of the general inventive concepts, the resin composition contains the microencapsulated curing agent and the non-microencapsulated curing agent in the ratio of from 0.5 to 5 parts per hundred parts resin by weight as the net amount of sum of all organic peroxides.
In one exemplary embodiment of the general inventive concepts, the resin composition contains the microencapsulated curing agent and the non-microencapsulated curing agent in the ratio of from 0.2 to 2 parts by weight to 1 part by weight, respectively, as the net amount of organic peroxide contained in each curing agent.
In one exemplary embodiment of the general inventive concepts, the resin composition further contains at least one additive selected from the group consisting of a low-shrinkage agent, a filler, a thickener, an anti-crack agent, an anti-separation agent, a mold release agent, and an inhibitor.
In one exemplary embodiment of the general inventive concepts, a manufacturing method for a fiber reinforced resin molded article comprises molding a molding compound by compression molding, wherein the molding compound comprises a resin composition and reinforcing fibers. The resin composition contains an unsaturated polyester resin, a microencapsulated curing agent, and a non-microencapsulated curing agent.
In one exemplary embodiment of the general inventive concepts, the microencapsulated curing agent of the molding compound used in the manufacturing method is a thermal responsive microencapsulated curing agent.
In one exemplary embodiment of the general inventive concepts, the non-microencapsulated curing agent of the molding compound used in the manufacturing method has a lower activity compared with the microencapsulated curing agent. In one exemplary embodiment of the general inventive concepts, the microencapsulated curing agent contains an organic peroxide having a one minute half-life temperature of 115° C. to 140° C., and the non-microencapsulated curing agent contains an organic peroxide having a one minute half-life temperature of 130° C. to 170° C. In one exemplary embodiment of the general inventive concepts, the microencapsulated curing agent contains an organic peroxide having a one minute half-life temperature of 120° C. to 130° C., and the non-microencapsulated curing agent contains an organic peroxide having a one minute half-life temperature of 140° C. to 160° C.
In one exemplary embodiment of the general inventive concepts, the resin composition of the molding compound used in the manufacturing method contains the microencapsulated curing agent and the non-microencapsulated curing agent in the ratio of from 0.5 to 5 parts per hundred parts resin by weight as the net amount of sum of all organic peroxides.
In one exemplary embodiment of the general inventive concepts, the resin composition of the molding compound used in the manufacturing method contains the microencapsulated curing agent and the non-micro encapsulated curing agent in the ratio of from 0.2 to 2 parts by weight to 1 part by weight, respectively, as the net amount of organic peroxide contained in each curing agent.
In one exemplary embodiment of the general inventive concepts, the resin composition of the molding compound used in the manufacturing method further contains at least one additive selected from the group consisting of a low-shrinkage agent, a filler, a thickener, an anti-crack agent, an anti-separation agent, a mold release agent, and an inhibitor.
The fiber reinforced resin molding compounds, according to the general inventive concepts, can exhibit a shelf life sufficient for practical use of the compounds after a reasonable storage period thereof.
The fiber reinforced resin molding compounds, according to the general inventive concepts, can retain flowability during the molding process such that the appearance of the resulting molded article is good.
The fiber reinforced resin molding compounds, according to the general inventive concepts, can be cured rapidly during the molding process, such that the overall molding time is shortened.
The fiber reinforced resin molding compounds, according to the general inventive concepts, can exhibit a high degree of cure, even for molded articles having a thickness in excess of 5 mm.
Numerous other aspects, advantages and/or features of the general inventive concepts, including equivalents thereof, will become more readily apparent from the following detailed description of exemplary embodiments and the claims presented herein.
DETAILED DESCRIPTION
The general inventive concepts relate to and contemplate fiber reinforced resin molding compounds and methods of manufacturing fiber reinforced resin molded articles therefrom. While the general inventive concepts are susceptible of embodiment in many different forms, there are described herein in detail specific embodiments thereof with the understanding that the present disclosure is to be considered as an exemplification of the principles of the general inventive concepts. Accordingly, the general inventive concepts are not intended to be limited to the specific embodiments described herein.
A molding compound for manufacturing a fiber reinforced molded article, according to one exemplary embodiment, comprises a resin composition and reinforcing fibers. The resin composition contains an unsaturated polyester resin, a microencapsulated curing agent and a non-microencapsulated curing agent.
In one exemplary embodiment, the resin composition contains the microencapsulated curing agent and the non-microencapsulated curing agent in the ratio of from 0.5 to 5 PHR (parts per hundred parts resin by weight) as the net amount of sum of all organic peroxides.
In one exemplary embodiment, the resin composition contains the microencapsulated curing agent and the non-microencapsulated curing agent in the ratio of from 0.2 to 2 parts by weight to 1 part by weight, respectively, as the net amount of organic peroxide contained in each curing agent.
Any microencapsulated curing agent providing the desired properties described herein can be used. For example, the microencapsulated curing agents described in the pending U.S. patent application having Ser. No. 13/436,161 and filed on Mar. 30, 2012 (published as U.S. 2012/0248639 on Oct. 4, 2012), the entire disclosure of which is incorporated herein by reference, can be used in this invention. As noted in the '639 publication, suitable curing agents can include, for example, dilauroyl peroxide, t-butyl peroxy-2-ethylhexanoate, 1,1,3,3-tetramethyl butylperoxy-2-ethylhexanoate, t-amyl-2-peroxy-2-ethylhexanoate and dibenzoyl peroxide.
The microencapsulated curing agents may be made by any known encapsulation technique. For example, the encapsulation techniques provided by Lyco Technologies, Inc. may suffice in forming the microencapsulated curing agents.
One exemplary encapsulation method, as described in the '639 publication, involves microencapsulating the curing agents in a polyurethane resin protective coating by means of interfacial polymerization. Interfacial polymerization is a process wherein a microcapsule wall of a polymer resin such as a polyamide, an epoxy resin, a polyurethane resin, a polyurea resin or the like is formed at an interface between two phases. The basic approach of the interfacial polymerization process is to (a) dissolve the peroxide curing agent and the isocyanate forming the polyurethane in an organic solvent which is essentially immiscible with water and a non-solvent for the polyol and optional polyamine forming the polyurethane, (b) emulsify the organic solution so formed in an aqueous phase by vigorous mixing, and then (c) add the polyol and optional polyamine to the emulsion so formed with continuous mixing to cause the polyurethane to form at the interface of the emulsified particles.
Forming microcapsules by interfacial polymerization is well-known and described in a number of publications. For example, such techniques are described in Masumi, et al., CREATION AND USE OF MICROCAPSULES, “1-3 Manufacturing Method and Use of Microcapsules,” Page 12-15, © 2005 by Kogyo Chosa Kai K.K. (ISBN4-7693-4194-6 C3058). Such techniques are also described in Mitsuyuki et al., APPLICATION AND DEVELOPMENT OF MICRO/NANO SYSTEM CAPSULE AND FINE PARTICLES, “4-3 Manufacturing method of Thermal Responsive Microcapsules,” Page 95-96, 2003 by K.K. CMC Shuppan (ISBN978-4-7813-0047-4 C3043).
In one exemplary embodiment, a thermal responsive microencapsulated curing agent is preferably used as the microencapsulated curing agent. When the thermal responsive microencapsulated curing agent is heated to a specific temperature that is required to practice a heat-press molding method, organic peroxide contained therein is emitted from the microcapsule.
In one exemplary embodiment, the microencapsulated curing agent desirably contains organic peroxide having a one minute half-life temperature of 115° C. to 140° C., and more desirably 120° C. to 130° C. As a result, the resin composition of the molding compound is rapidly cured during the molding process, so molding time is shortened.
Any non-microencapsulated curing agent providing the desired properties described herein can be used. For example, the non-microencapsulated curing agent can be a curing agent that is normally used for a conventional fiber reinforced resin molding compound, such as SMC. The non-microencapsulated curing agent can be a liquid, powder or particle.
In one exemplary embodiment, the non-microencapsulated curing agent has a lower activity compared with the microencapsulated curing agent. As a result, a problem of a shortened shelf life of the molding compound is prevented.
In one exemplary embodiment, for the compatibility of activity of the curing agent with sufficient shelf life of the molding compound, the non-microencapsulated curing agent desirably contains organic peroxide having a one minute half-life temperature of 130° C. to 170° C., and more desirably 140° C. to 160° C. As these non-microencapsulated curing agents, 1,1-di(t-hexylperoxy)cyclohexane (one minute half-life temperature: 149° C.), t-Amyl peroxy isopropyl carbonate (one minute half-life temperature: 153° C.), t-butyl peroxy isopropyl monocarbonate (one minute half-life temperature: 159° C.), t-butyl peroxy benzoate (one minute half-life temperature: 169° C.) or a mixture of at least two organic peroxides selected from above can, for example, be used.
By combining the microencapsulated curing agent and the non-microencapsulated curing agent, sufficient activity of the curing agents is obtained, and flowability of the molding compound can be retained during the molding process. As a result, even in a case where a molding time of a thick molded article is short, a sufficient degree of cure can be obtained, and the appearance of the resulting molded article is good.
In one exemplary embodiment, the total amount of the microencapsulated curing agent and the non-microencapsulated curing agent contained in the unsaturated polyester resin composition should be sufficient, so that the net amount of sum of all organic peroxides present is about 0.5 to 5 PHR, more typically 0.8 to 4 PHR, or even 0.9 to 3 PHR. PHR means “parts per hundred parts resin by weight,” namely a ratio of the additive to the resin ingredients of 100 parts by weight. In this unit, the resin ingredients are the sum of the unsaturated polyester resin and the low shrinkage additive.
In one exemplary embodiment, for the compatibility of activity of the curing agent with flowability of the molding compound, the ratio of the microencapsulated curing agent to the non-microencapsulated curing agent preferably is 0.2 to 2 parts by weight to 1 part by weight, and more preferably is 0.3 to 1.5 parts by weight to 1 part by weight. This ratio is expressed by the net amount of organic peroxide contained in each curing agent.
As noted above, the molding compound for manufacturing a fiber reinforced molded article, according to one exemplary embodiment, comprises a resin composition and reinforcing fibers. The resin composition contains an unsaturated polyester resin, the above mentioned microencapsulated curing agent, and the non-microencapsulated curing agent. And the resin composition can further contain at least one additive selected from the group consisting of a low-shrinkage agent, a filler, a thickener, an anti-crack agent, an anti-separation agent, a mold release agent, and an inhibitor. The unsaturated polyester resin and/or these additives can be the same as the resins and additives that are used in conventional molding compounds such as SMC.
In one exemplary embodiment, the reinforcing fibers are glass fibers. In one exemplary embodiment, the glass fibers have a filament diameter of 5-20 μm. Such glass fibers can be continuous or chopped, and if chopped desirably have a length of 20-100 mm. In addition, such filaments can also be formed into strands. In one exemplary embodiment, the reinforcing fibers are strands having a yarn count (weight per unit length) of 50-5,000 gm/km. In one exemplary embodiment, the reinforcing fibers are strands having a bundling number of 50-200 filaments per strand. If desired, such glass fibers, and/or the strands and yarns made therefrom, can be coated with a suitable sizing agent containing a silane coupling agent, the sizing agent also optionally containing a film-forming agent such as a polyurethane or polyvinyl acetate resin, and other conventional ingredients such as cationic and nonionic surfactants and the like. In one exemplary embodiment, a sizing amount of 0.2-2 wt. %, based on the weight of the glass fiber being coated, is applied.
In one exemplary embodiment, the reinforcing fibers are non-glass fibers, such as carbon fibers.
Any amount of the reinforcing fibers can be included in the thermosetting resin molding compounds. In one exemplary embodiment, a reinforcing fiber concentration on the order of 10-60 wt. %, and more preferably 20-50 wt. %, based on the weight of the thermosetting composition as a whole, is used.
The molding compounds of the general inventive concepts can have a form such as sheet molding compounds (“SMC”), bulk molding compounds (“BMC”), or thick molding compounds (“TMC”).
In one exemplary embodiment, a manufacturing method for a fiber-reinforced resin molded article involves these molding compounds being molded to obtain the molded article, such as by a compression molding method.
Tables 1 and 2 illustrate various working examples of molding compounds that comport with the general inventive concepts described herein. In particular, resin compositions having formulations described in Table 2 were prepared, and curing agents mentioned in Table 1 were used in these compositions.
TABLE 1
Type and Composition of Curing Agent
Name of curing agent CA-1 CA-C CA-D
Type microencapsulated non- non-
microencapsulated microencapsulated
Form dried powder liquid liquid
Shell material polyurethane resin — —
Peroxide t-Amyl peroxy 2- t-Amyl peroxy 2- mixture mainly
ethylhexanoate ethylhexanoate containing t-Butyl
peroxy isopropyl
monocarbonate
One minute half life temperature (° C.) 127 127 156
Producing method of microcapsule interfacial — —
polymerization
Peroxide content (wt %) 34.5  50  92
Average particle diameter (μm) 90 — —
TABLE 2
Formulation of Resin Composition Unit: wt %
Name of composition
Resin Resin Resin Resin
Com- Com- Com- Com- Resin Resin Resin Resin
position-1 position-2 position-3 position-V Composition-W Composition-X Composition-Y Composition-Z
Name of microencapsulated CA-1 CA-1 CA-1 CA-1 CA-1 CA-1 — —
curing agent
Name of non-microencapsulated CA-D CA-D CA-D CA-C — — CA-D CA-C
curing agent
Unsaturated polyester resin 32.96 33.03 32.80 32.96 32.92 32.56 33.07 33.04
Low shrinkage additive 10.99 11.01 10.93 10.99 10.97 10.85 11.02 11.01
(polystyrene)
Pigment (gray color) 2.07 2.07 2.06 2.07 2.06 2.04 2.07 2.07
Microencapsulated curing agent 0.44 0.44 0.88 0.44 1.10 2.17 0.00 0.00
Non-microencapsulated curing 0.44 0.22 0.44 0.44 0.00 0.00 0.44 0.75
agent
Inhibitor (MEK solution of p- 0.11 0.11 0.11 0.11 0.00 0.00 0.22 0.00
benzoquinone, 5 wt % conc.)
Mold releasing agent (zinc 2.20 2.20 2.19 2.20 2.19 2.17 2.20 2.20
stearate)
Anti-crack agent (polyethylene) 1.76 1.76 1.75 1.76 1.76 1.74 1.76 1.76
Filler (calcium carbonate) 48.32 48.45 48.13 48.32 48.29 47.77 48.51 48.46
Anti-separation agent 0.18 0.18 0.18 0.18 0.18 0.17 0.18 0.18
Thickener (magnesium oxide) 0.53 0.53 0.53 0.53 0.53 0.53 0.53 0.53
Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00
Ratio of total net amount of 1.25 0.79 1.60 0.84 0.87 1.73 0.91 0.86
peroxide/PHR
Ratio of non-MC to MC in net 1:0.38 1:0.75 1:0.75 1:0.68 — — 1:0 1:0
amount of peroxide/PBW
Table 3 relates to evaluating the samples for shelf life. The resin compositions were individually put in steel can with a cap, and they were aged under atmosphere at a temperature of 40° C. over two days. Then, they were kept under room temperature. After a specific amount of time had passed, the condition of each resin composition was visually inspected and evaluated by criteria noted in Table 3. The results obtained are set forth in the following Table 3.
Accordingly, it is understood that the exemplary molding compounds of the general inventive concepts have sufficient shelf life as lengthy as a conventional molding compound using Resin Composition-Y, because inventive Resin Composition-1 has sufficient flowability even after 101 days passed. Furthermore, it is understood that the shelf life of the molding compounds using Resin Composition-V or Resin Composition-Z, which contain a non-microencapsulated curing agent with high activity, is so short as to be impractical.
TABLE 3
Evaluation for shelf life of resin compositions
Name of composition
Resin Resin Resin Resin Resin Resin
Composition-1 Composition-V Composition-W Composition-X Composition-Y Composition-Z
Name of microencapsulated CA-1 CA-1 CA-1 CA-1 — —
curing agent
Name of non-microencapsulated CA-D CA-C — — CA-D CA-C
curing agent
Days passed after preparation of
resin composition Condition of resin compositions
 1 OK OK OK OK OK OK
 2 OK OK OK OK OK NG
 7 OK NG OK OK OK NG
 27 OK NG OK OK OK NG
 55 OK NG OK OK OK NG
101 OK NG OK OK OK NG
“OK”: having flowability sufficient to mold as molding compound
“NG”: hardened or gelled as high viscosity as can not be used
Table 4 relates to evaluating the samples for moldability (curing speed) in the context of a SMC. In particular, Resin Composition-1 was formulated into a sheet molding compound (SMC-1) by combining 66 wt. % of a chopped glass fiber strand having a length of about 25 mm, the chopped glass fiber strand being made from a glass fiber strand having a linear density of 75 gm/km, a bundling number of 150 filaments per strand and a filament diameter of 16 μm, the glass fiber strand being sized with 0.95 wt. % of a sizing agent containing a silane coupling agent, a polyurethane resin and a polyvinyl acetate resin. In the same way, Resin Composition-V to Resin Composition-Z were formulated into a sheet molding compound (SMC-V to SMC-Z) by combining 66 wt. % of each molding resin with 34 wt. % of the same chopped glass fiber strand used to make sheet molding compound SMC-1.
Each of the sheet molding compounds so made was then molded into a flat plate having a thickness of 3 mm or 5 mm by means of a heat-press molding machine in which an upper platen heated to a temperature of 140° C. and a lower platen heated to 145° C. were compressed together at a cylinder pressure of 180 kg/cm2. After a specific amount of time under these conditions, the platens were opened, and the molded plates were visually inspected for surface appearance and condition of cure. Then, according to the criteria noted in Table 4, surface appearance and condition of cure were evaluated. The results obtained are set forth in the following Table 4. In the case where the flat plate having a thickness of 3 mm is molded at a time of 60 seconds, a curing condition of SMC other than SMC-W containing only a small amount of the microencapsulated curing agent and SMC-Y as conventional SMC is sufficient.
It takes a time of 130 seconds, as a standard molding time, to make the flat plate having a thickness of 5 mm from SMC-Y, which is a conventional SMC. In contrast, only SMC-1 as an exemplary inventive SMC was cured sufficiently in a time shorter than this standard molding time, such as 90, 70, and 60 seconds. This evidences a more rapid cure of SMC. In SMC-V, namely SMC containing the microencapsulated curing agent and the non-microencapsulated curing agent, both having high activity, its cure condition was poor.
TABLE 4
Evaluation of SMC
Name of sheet molding compound
SMC-1 SMC-V SMC-W SMC-X SMC-Y SMC-Z
Name of microencapsulated CA-1 CA-1 CA-1 CA-1 — —
curing agent
Name of non- CA-D CA-C — — CA-D CA-C
microencapsulated curing agent
Name of resin composition Resin Resin Resin Resin Resin Resin
Composition-1 Composition-V Composition-W Composition-X Composition-Y Composition-Z
Glass fiber content (wt. %) 34 34 34 34 34 34
Compressing time (sec.) Test results of molding flat plates having thickness of 3 mm
 60 cured cured not cured cured not cured cured
Compressing time (sec.) Test results of molding flat plates having thickness of 5 mm
130*1 cured (not tested) not cured (not tested) cured (not tested)
 90 cured not cured not cured not cured not cured not cured
 70 cured not cured (not tested) not cured not cured cured, but poor
smoothness
 60 cured (not tested) (not tested) (not tested) not cured (not tested)
*1standard molding time of conventional SMC such as SMC Y
“cured”: SMC has sufficiently cured in whole, and molded flat plate has good surface appearance
“not cured”: SMC has not cured in its inside, or delaminated portion such as air gap has remained in molded flat plate
Table 5 relates to evaluating the SMC samples for cure time. In particular, Cure Time of SMC was measured by the method using the equipment having the name of “Cure Tool.” Test conditions and the results obtained are set forth in the following Table 5. Cure Time means the required time until reaching the highest temperature from start of heating. As noted in Table 5, the Cure Time of SMC-1, SMC-2 and SMC-3, as inventive SMCs, are shorter than SMC-Y, as a conventional SMC.
TABLE 5
Evaluation of SMC <Cure Time>
Name of sheet molding compound
SMC-1 SMC-2 SMC-3 SMC-V SMC-W SMC-X SMC-Y SMC-Z
Name of microencapsulated CA-1 CA-1 CA-1 CA-1 CA-1 CA-1 — —
curing agent
Name of non- CA-D CA-D CA-D CA-C — — CA-D CA-C
microencapsulated
curing agent
Name of resin composition Resin Resin Resin Resin Resin Resin Resin Resin
Com- Com- Com- Composition-V Composition-W Composition-X Composition-Y Composition-Z
position-1 position-1 position-1
Glass fiber content (wt. %) 34 34 34 34 34 34 34 34
Cure time* (sec.) 89.8 93.0 85.5 70.0 80.0 68.7 109.0 63.0
Test method: using test equipment having name of “Cure Tool”
Test condition: platen temperature (upper/lower) 145° C./145° C., pressure: 125 kgf/cm2, mold size: 70 cm suquare, charge amount of SMC: 65 grams
*Cure time: the required time until reaching the highest temperature from start of heating
Table 6 relates to evaluating the SMC samples for specular glossiness. In particular, specular glossiness of molded articles made from the above-mentioned SMCs was measured by the method according to JIS Z8741, on an incident angle of 60 degrees. The results obtained are set forth in the following Table 6. In a conventional SMC, namely SMC-Y, the glossiness of its molded article tends to decline with shortening of compressing time. On the other hand, all of the molded articles made from SMC-1, as an inventive SMC, have glossiness equivalent to the molded article made from conventional SMC by the standard molding time.
TABLE 6
Evaluation of SMC <Specular glossiness>
Name of sheet molding compound
SMC-1 SMC-V SMC-W SMC-X SMC-Y SMC-Z
Name of microencapsulated CA-1 CA-1 CA-1 CA-1 — —
curing agent
Name of non- CA-D CA-C — — CA-D CA-C
microencapsulated curing agent
Name of resin composition Resin Resin Resin Resin Resin Resin
Composition-1 Composition-V Composition-W Composition-X Composition-Y Composition-Z
Glass fiber content (wt. %) 34   34   34   34   34   34  
Compressing time (sec.) Test results of molding flat plates having thickness of 5 mm
130*1 76.3 (not tested) 51.6 (not tested) 75.1 (not tested)
 90 75.7 57.2 41.0 51.8 60.9 48.9
 70 61.4 55.7 (not tested) 51.4 51.1 39.8
 60 64.4 (not tested) (not tested) (not tested) 45.9 (not tested)
*1standard molding time of conventional SMC such as SMC Y
Test method: JIS Z8741, “Gs(60°)” as a measurement on incident angle of 60 degrees
Tables 7 and 8 relate to evaluating the SMC samples for bending strength and bending modulus, respectively. In particular, bending strength and bending modulus of molded articles made from SMC-1 and SMC-4, as exemplary inventive SMC, and SMC-Y, as a conventional SMC, were measured. Test conditions and the results obtained are set forth in the following Table 7 and Table 8.
In SMC-1, both properties tend to decrease with shortening of compressing time. This tendency was resolved by SMC-4 having a relatively high glass fiber content.
TABLE 7
Evaluation of SMC <Bending strengths> Unit: MPa
Name of sheet molding compound SMC - 1 SMC - 4 SMC - Y
Name of microencapsulated CA-1 CA-1 —
curing agent
Name of non-microencapsulated CA-D CA-D CA-D
curing agent
Name of resin composition Resin Resin Resin
Composition - 1 Composition - 1 Composition - Y
Glass fiber content (wt. %) 34  36  34 
Compressing time (sec.) Test results of molding flat plates having thickness of 5 mm
130 *1 155.4 (not tested) 155.2
 90 139.3 151.1 134.0
 70 144.1 168.6 (not tested)
 60 (not tested) 169.2 (not tested)
*1 standard molding time of conventional SMC such as SMC-Y
Test condition
Specimen size: width 10 mm, length 110 mm, thickness 5 mm
Head speed: 3 mm/min.
Span: 80 mm
TABLE 8
Evaluation of SMC <Bending modulus> Unit: GPa
Name of sheet molding compound SMC - 1 SMC - 4 SMC - Y
Name of microencapsulated CA-1 CA-1 —
curing agent
Name of non-microencapsulated CA-D CA-D CA-D
curing agent
Name of resin composition Resin Resin Resin
Composition - 1 Composition - 1 Composition - Y
Glass fiber content (wt. %) 34   36   34  
Compressing time (sec.) Test results of molding flat plates having thickness of 5 mm
130 *1 11.2 (not tested) 10.5
 90 14.1 10.8  9.6
 70  9.7 11.2 (not tested)
 60 (not tested) 11.7 (not tested)
*1 standard molding time of conventional SMC such as SMC-Y
Test condition
Specimen size: width 10 mm, length 110 mm, thickness 5 mm
Head speed: 3 mm/min
Span: 80 mm
In view of the above, the inventive fiber reinforced resin molding compounds have been shown to provide superior properties over those presented by conventional fiber reinforced resin molding compounds. For example, SMC-1, as an exemplary inventive molding compound, obtained excellent results in both shelf life and curing condition.
The general inventive concepts further contemplate manufacturing methods for producing fiber reinforced resin molded articles, the manufacturing methods using any of the fiber reinforced resin molding compounds described or suggested herein.
The above description of specific embodiments has been given by way of example. From the disclosure given, those skilled in the art will not only understand the general inventive concepts and their attendant advantages, but will also find apparent various changes and modifications to the compounds and methods disclosed. It is sought, therefore, to cover all such changes and modifications as fall within the spirit and scope of the general inventive concepts, as described and claimed herein, and any equivalents thereof.

Claims (7)

The invention claimed is:
1. A molding compound comprising a resin composition and reinforcing fibers, wherein the resin composition contains an unsaturated polyester resin, a microencapsulated curing agent and a non-microencapsulated curing agent,
wherein the non-microencapsulated curing agent has a longer curing time compared with the microencapsulated curing agent,
wherein the microencapsulated curing agent contains an organic peroxide having a one minute half-life temperature of 115° C. to 130° C.; and wherein the non-microencapsulated curing agent contains an organic peroxide having a one minute half-life temperature of 140° C. to 170° C.
2. The molding compound of claim 1, wherein the microencapsulated curing agent is a thermal responsive microencapsulated curing agent.
3. The molding compound of claim 1, wherein the resin composition contains the microencapsulated curing agent and the non-microencapsulated curing agent in the ratio of from 0.5 to 5 parts per hundred parts resin by weight as the net amount of sum of all organic peroxides.
4. The molding compound of claim 1, wherein the resin composition contains the microencapsulated curing agent and the non-microencapsulated curing agent in the ratio of from 0.2 to 2 parts by weight to 1 part by weight, respectively, as the net amount of organic peroxide contained in each curing agent.
5. The molding compound of claim 1, wherein the resin composition further contains at least one additive selected from the group consisting of a low-shrinkage agent, a filler, a thickener, an anti-crack agent, an anti-separation agent, a mold release agent, and an inhibitor.
6. The molding compound of claim 1, wherein said non-microencapsulated curing agent is selected from the group consisting of: 1,1-di(t-hexylperoxy)cyclohexane, t-Amyl peroxy isopropyl carbonate, t-butyl peroxy isopropyl monocarbonate, t-butyl peroxy benzoate; and a mixture thereof.
7. A manufacturing method for a fiber reinforced resin molded article comprising molding the molding compound according to claim 1 by compression molding.
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* Cited by examiner, † Cited by third party
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JP2017524785A (en) * 2014-08-12 2017-08-31 オーシーヴィー インテレクチュアル キャピタル リミテッド ライアビリティ カンパニー Conductive sheet molding compound
JP2016103415A (en) * 2014-11-28 2016-06-02 株式会社オートネットワーク技術研究所 Cable with terminal

Citations (66)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3142666A (en) * 1959-03-05 1964-07-28 Monsanto Co Ethylene polymerization utilizing two organic peroxygen compounds as catalysts
US3395105A (en) 1964-10-06 1968-07-30 Mc Donnell Douglas Corp Epoxy systems containing encapsulated pressure fracturable curing agents
GB1148635A (en) 1966-02-04 1969-04-16 Wallace & Tiernan Inc Encapsulating liquids or solids
JPS4819545B1 (en) 1970-12-22 1973-06-14
GB1331286A (en) 1970-10-15 1973-09-26 Kodak Ltd Diazonaphthalene compounds
US3892581A (en) 1973-09-10 1975-07-01 Ppg Industries Inc Glass fiber compositions
JPS5277003A (en) 1975-12-24 1977-06-29 Nippon Oil & Fats Co Ltd Stabilization process of peroxyketones
US4080238A (en) 1976-07-14 1978-03-21 Pratt & Lambert, Inc. One-liquid cold setting adhesive with encapsulated catalyst initiator
GB1539809A (en) 1975-08-14 1979-02-07 Hinterwaldner Rudolf Hardenable composition method of producing and hardening same and its application
US4154774A (en) 1975-08-04 1979-05-15 Rudolf Hinterwaldner Adhesive, gluing, putty, sealer and coating materials from (1) hardenable component, (2) metal salt and (3) pulverulent olefin polymer
JPS5676432A (en) 1979-11-24 1981-06-24 Mitsubishi Petrochem Co Ltd Sheet molding compound
US4303736A (en) 1979-07-20 1981-12-01 Leonard Torobin Hollow plastic microspheres
JPS5712017A (en) 1980-06-25 1982-01-21 Mitsubishi Petrochem Co Ltd Unsaturated polyester resin composition
US4362566A (en) 1977-03-10 1982-12-07 Rudolf Hinterwaldner One-component hardenable substances stable to storage and activatable by mechanical and/or physical forces and method of producing, activating and applying same
US4428983A (en) 1980-10-16 1984-01-31 Bayer Aktiengesellschaft Process for the production of microcapsules
WO1984001919A1 (en) 1982-11-12 1984-05-24 Dougherty Michael J Process for the manufacture of products from reinforced polyester resins
JPS6028449A (en) 1983-07-27 1985-02-13 Mitsubishi Gas Chem Co Inc Unsaturated polyester resin composition
US4528354A (en) 1984-04-25 1985-07-09 Mcdougal John R Process and composition for the manufacture of products from silicone rubber
JPS60139331A (en) 1983-12-27 1985-07-24 Sanken Kako Kk Stabilized organic peroxide composition
US4547429A (en) 1983-09-17 1985-10-15 Cassella Aktiengesellschaft Encapsulated salts of acid particles wherein the salt particles are surrounded by a polyurethane/polyurea casing
US4622267A (en) 1983-12-23 1986-11-11 Feldmuhle Aktiengesellschaft Microcapsules having capsule walls formed of aliphatic diisocyanate and diamine
JPS634919A (en) 1986-06-25 1988-01-09 Matsushita Electric Works Ltd Heat-compression molding device for plastic
EP0287288A1 (en) 1987-04-14 1988-10-19 Interox Chemicals Limited Curing polyester resins
US4808639A (en) 1986-07-16 1989-02-28 Production Previews, Inc. Liquid curable adhesive composition comprising a polyester resin and a microencapsulated peroxide curing agent
US4876296A (en) 1987-04-27 1989-10-24 Olin Corporation Method and composition for controlled thickening of thermosetting resins using microencapsulated thickeners
JPH01282250A (en) 1988-05-07 1989-11-14 Fuji Kobunshi Kk Low-temperature curing unsaturated polyester resin composition
JPH0252038A (en) 1988-08-15 1990-02-21 Toagosei Chem Ind Co Ltd Capsule body and preparation thereof
JPH0258546A (en) 1988-08-24 1990-02-27 Mitsubishi Plastics Ind Ltd Molding method for resin-impregnated fiber sheet molded products
JPH0343244A (en) 1989-07-12 1991-02-25 Kuraray Co Ltd Damping metal composite body
US5084494A (en) * 1982-11-12 1992-01-28 Mcdougal John R Polyester resin and reinforcement composite materials
JPH04175321A (en) 1990-11-09 1992-06-23 Nippon Oil & Fats Co Ltd Microencapsulated curing agent, its production, unsaturated polyester resin composition containing said agent, its curing, and its stabilization
US5132052A (en) 1991-03-20 1992-07-21 Gencorp Inc. Fast cure in-mold coating
JPH04372644A (en) 1991-06-24 1992-12-25 Matsushita Electric Works Ltd Phenolic resin composition
JPH0578411A (en) 1991-09-19 1993-03-30 Nippon Oil & Fats Co Ltd Microencapsulated curing agent, its production, unsaturated polyester resin composition containing the same curing agent and method for curing and stabilizing the same
JPH05138793A (en) 1991-11-21 1993-06-08 Sumitomo Bakelite Co Ltd Manufacture of phenol ic resin laminate
EP0552976A1 (en) 1992-01-22 1993-07-28 W.R. Grace & Co.-Conn. Spherical potential curing agent for epoxy resin and preparation thereof
WO1993015131A2 (en) 1992-01-17 1993-08-05 Brian Burnett Chandler Curable resin systems and applications thereof
JPH069802A (en) 1992-06-26 1994-01-18 Mitsubishi Rayon Co Ltd Prepreg
JPH06100638A (en) 1992-09-22 1994-04-12 Nippon Oil & Fats Co Ltd Unsaturated polyester resin composition
JPH0790907A (en) 1993-09-22 1995-04-04 Matsushita Electric Ind Co Ltd Heating toilet seat device
JPH07304968A (en) 1994-03-15 1995-11-21 Toray Ind Inc Microencapsulated curing agent, production thereof, thermosetting resin composition, prepreg, and fiber-reinforced composite material
JPH0812861A (en) 1994-06-30 1996-01-16 Mitsubishi Chem Corp Epoxy resin composition and prepreg
JPH0820708A (en) 1994-07-06 1996-01-23 Mitsubishi Chem Corp Epoxy resin composition and prepreg using the same
JPH0841174A (en) 1994-08-01 1996-02-13 Mitsubishi Chem Corp Epoxy resin composition and prepreg
US5589523A (en) 1994-03-15 1996-12-31 Toray Industries, Inc. Microcapsule-type curing agent, method for producing the same, thermosetting resin composition, prepreg and fiber reinforced composite material
JPH1143618A (en) 1997-07-25 1999-02-16 Kayaku Akzo Kk Curing agent composition
JPH1190399A (en) 1997-09-16 1999-04-06 Sanyo Electric Co Ltd Organic matter treating apparatus
JP2001114757A (en) 1999-10-12 2001-04-24 Kayaku Akzo Corp Alkylperoxymethyl-substituted benzoate, resin composition and molded product
JP2001302760A (en) 2000-04-21 2001-10-31 Mitsubishi Rayon Co Ltd Epoxy resin composition
JP2001316451A (en) 2000-05-08 2001-11-13 Asahi Chem Res Lab Ltd Epoxy resin composition
WO2002016482A2 (en) 2000-08-18 2002-02-28 Huntsman International Llc One component thermoset polyurethane system
JP2002524634A (en) 1998-09-12 2002-08-06 ケムコロイズ・リミテッド Resin curing method
US6555602B1 (en) 1999-10-06 2003-04-29 Nitto Denko Corporation Composition of epoxy resin, anhydride and microcapsule accelerator
JP2003253089A (en) 2002-02-07 2003-09-10 Bakelite Ag Thermosetting resin-fiber composite and manufacturing method and apparatus therefor
WO2003086611A1 (en) 2002-04-15 2003-10-23 Schenectady International Inc. Microcapsules for the production of storage-stable unsaturated polymer compositions
JP2004075914A (en) 2002-08-21 2004-03-11 Toray Ind Inc Epoxy resin composition and prepreg
US20040242346A1 (en) 2003-05-29 2004-12-02 Keiji Ohama Golf ball and method of manufacturing the same
US20050058822A1 (en) 2003-08-04 2005-03-17 Ittel Steven Dale Fiber-reinforced thermoplastic matrices
JP2005226014A (en) 2004-02-13 2005-08-25 Showa Highpolymer Co Ltd Resin composition for pultrusion, fiber-reinforced resin composition, method for molding the same and molded article
JP4175321B2 (en) 2004-12-01 2008-11-05 株式会社デンソー Pointer instrument
JP4372644B2 (en) 2004-08-25 2009-11-25 カルソニックカンセイ株式会社 Airbag control device
US7959838B2 (en) 2002-11-28 2011-06-14 Mitsubishi Rayon Co., Ltd. Epoxy resin for prepreg, prepreg, fiber-reinforced composite material and methods for production thereof
WO2011073111A1 (en) 2009-12-14 2011-06-23 Gurit (Uk) Ltd Prepregs for manufacturing composite materials
JP5078411B2 (en) 2007-03-31 2012-11-21 財団法人福岡県産業・科学技術振興財団 Integrated circuit module
JP5138793B2 (en) 2011-06-01 2013-02-06 株式会社サンセイアールアンドディ Game machine
US8715543B2 (en) 2011-03-31 2014-05-06 Ocv Intellectual Capital, Llc Microencapsulated curing agent

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4524043A (en) * 1982-11-12 1985-06-18 Mcdougal John R Process for the manufacture of products from reinforced polyester resins
JP2004269573A (en) * 2003-03-05 2004-09-30 Showa Highpolymer Co Ltd Sheet molding compound
KR101160352B1 (en) * 2004-03-26 2012-06-26 김도균 Highly functional resin recycled polyester and polyamide hybrid waste and its manufacturing method

Patent Citations (70)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3142666A (en) * 1959-03-05 1964-07-28 Monsanto Co Ethylene polymerization utilizing two organic peroxygen compounds as catalysts
US3395105A (en) 1964-10-06 1968-07-30 Mc Donnell Douglas Corp Epoxy systems containing encapsulated pressure fracturable curing agents
GB1148635A (en) 1966-02-04 1969-04-16 Wallace & Tiernan Inc Encapsulating liquids or solids
GB1331286A (en) 1970-10-15 1973-09-26 Kodak Ltd Diazonaphthalene compounds
JPS4819545B1 (en) 1970-12-22 1973-06-14
US3892581A (en) 1973-09-10 1975-07-01 Ppg Industries Inc Glass fiber compositions
US4154774A (en) 1975-08-04 1979-05-15 Rudolf Hinterwaldner Adhesive, gluing, putty, sealer and coating materials from (1) hardenable component, (2) metal salt and (3) pulverulent olefin polymer
GB1539809A (en) 1975-08-14 1979-02-07 Hinterwaldner Rudolf Hardenable composition method of producing and hardening same and its application
JPS5277003A (en) 1975-12-24 1977-06-29 Nippon Oil & Fats Co Ltd Stabilization process of peroxyketones
US4080238A (en) 1976-07-14 1978-03-21 Pratt & Lambert, Inc. One-liquid cold setting adhesive with encapsulated catalyst initiator
US4362566A (en) 1977-03-10 1982-12-07 Rudolf Hinterwaldner One-component hardenable substances stable to storage and activatable by mechanical and/or physical forces and method of producing, activating and applying same
US4303736A (en) 1979-07-20 1981-12-01 Leonard Torobin Hollow plastic microspheres
JPS5676432A (en) 1979-11-24 1981-06-24 Mitsubishi Petrochem Co Ltd Sheet molding compound
JPS5712017A (en) 1980-06-25 1982-01-21 Mitsubishi Petrochem Co Ltd Unsaturated polyester resin composition
US4428983A (en) 1980-10-16 1984-01-31 Bayer Aktiengesellschaft Process for the production of microcapsules
JPS59502018A (en) 1982-11-12 1984-12-06 マツクドウガル，ジヨン　ア−ル． Manufacturing method for reinforced polyester resin products
WO1984001919A1 (en) 1982-11-12 1984-05-24 Dougherty Michael J Process for the manufacture of products from reinforced polyester resins
US5084494A (en) * 1982-11-12 1992-01-28 Mcdougal John R Polyester resin and reinforcement composite materials
JPS6028449A (en) 1983-07-27 1985-02-13 Mitsubishi Gas Chem Co Inc Unsaturated polyester resin composition
US4547429A (en) 1983-09-17 1985-10-15 Cassella Aktiengesellschaft Encapsulated salts of acid particles wherein the salt particles are surrounded by a polyurethane/polyurea casing
US4622267A (en) 1983-12-23 1986-11-11 Feldmuhle Aktiengesellschaft Microcapsules having capsule walls formed of aliphatic diisocyanate and diamine
JPS60139331A (en) 1983-12-27 1985-07-24 Sanken Kako Kk Stabilized organic peroxide composition
US4528354A (en) 1984-04-25 1985-07-09 Mcdougal John R Process and composition for the manufacture of products from silicone rubber
JPS634919A (en) 1986-06-25 1988-01-09 Matsushita Electric Works Ltd Heat-compression molding device for plastic
US4808639A (en) 1986-07-16 1989-02-28 Production Previews, Inc. Liquid curable adhesive composition comprising a polyester resin and a microencapsulated peroxide curing agent
EP0287288A1 (en) 1987-04-14 1988-10-19 Interox Chemicals Limited Curing polyester resins
US4876296A (en) 1987-04-27 1989-10-24 Olin Corporation Method and composition for controlled thickening of thermosetting resins using microencapsulated thickeners
JPH01282250A (en) 1988-05-07 1989-11-14 Fuji Kobunshi Kk Low-temperature curing unsaturated polyester resin composition
JPH0252038A (en) 1988-08-15 1990-02-21 Toagosei Chem Ind Co Ltd Capsule body and preparation thereof
JPH0258546A (en) 1988-08-24 1990-02-27 Mitsubishi Plastics Ind Ltd Molding method for resin-impregnated fiber sheet molded products
JPH0343244A (en) 1989-07-12 1991-02-25 Kuraray Co Ltd Damping metal composite body
JPH04175321A (en) 1990-11-09 1992-06-23 Nippon Oil & Fats Co Ltd Microencapsulated curing agent, its production, unsaturated polyester resin composition containing said agent, its curing, and its stabilization
US5132052A (en) 1991-03-20 1992-07-21 Gencorp Inc. Fast cure in-mold coating
JPH04372644A (en) 1991-06-24 1992-12-25 Matsushita Electric Works Ltd Phenolic resin composition
JPH0578411A (en) 1991-09-19 1993-03-30 Nippon Oil & Fats Co Ltd Microencapsulated curing agent, its production, unsaturated polyester resin composition containing the same curing agent and method for curing and stabilizing the same
JPH05138793A (en) 1991-11-21 1993-06-08 Sumitomo Bakelite Co Ltd Manufacture of phenol ic resin laminate
WO1993015131A2 (en) 1992-01-17 1993-08-05 Brian Burnett Chandler Curable resin systems and applications thereof
EP0552976A1 (en) 1992-01-22 1993-07-28 W.R. Grace & Co.-Conn. Spherical potential curing agent for epoxy resin and preparation thereof
US5357008A (en) 1992-01-22 1994-10-18 W. R. Grace & Co.-Conn. Latent curing agent for epoxy resin and its preparation
JPH069802A (en) 1992-06-26 1994-01-18 Mitsubishi Rayon Co Ltd Prepreg
JPH06100638A (en) 1992-09-22 1994-04-12 Nippon Oil & Fats Co Ltd Unsaturated polyester resin composition
JPH0790907A (en) 1993-09-22 1995-04-04 Matsushita Electric Ind Co Ltd Heating toilet seat device
US5589523A (en) 1994-03-15 1996-12-31 Toray Industries, Inc. Microcapsule-type curing agent, method for producing the same, thermosetting resin composition, prepreg and fiber reinforced composite material
JPH07304968A (en) 1994-03-15 1995-11-21 Toray Ind Inc Microencapsulated curing agent, production thereof, thermosetting resin composition, prepreg, and fiber-reinforced composite material
JPH0812861A (en) 1994-06-30 1996-01-16 Mitsubishi Chem Corp Epoxy resin composition and prepreg
JPH0820708A (en) 1994-07-06 1996-01-23 Mitsubishi Chem Corp Epoxy resin composition and prepreg using the same
JPH0841174A (en) 1994-08-01 1996-02-13 Mitsubishi Chem Corp Epoxy resin composition and prepreg
JPH1143618A (en) 1997-07-25 1999-02-16 Kayaku Akzo Kk Curing agent composition
JPH1190399A (en) 1997-09-16 1999-04-06 Sanyo Electric Co Ltd Organic matter treating apparatus
JP2002524634A (en) 1998-09-12 2002-08-06 ケムコロイズ・リミテッド Resin curing method
US6555602B1 (en) 1999-10-06 2003-04-29 Nitto Denko Corporation Composition of epoxy resin, anhydride and microcapsule accelerator
JP2001114757A (en) 1999-10-12 2001-04-24 Kayaku Akzo Corp Alkylperoxymethyl-substituted benzoate, resin composition and molded product
JP2001302760A (en) 2000-04-21 2001-10-31 Mitsubishi Rayon Co Ltd Epoxy resin composition
JP2001316451A (en) 2000-05-08 2001-11-13 Asahi Chem Res Lab Ltd Epoxy resin composition
WO2002016482A2 (en) 2000-08-18 2002-02-28 Huntsman International Llc One component thermoset polyurethane system
JP2003253089A (en) 2002-02-07 2003-09-10 Bakelite Ag Thermosetting resin-fiber composite and manufacturing method and apparatus therefor
WO2003086611A1 (en) 2002-04-15 2003-10-23 Schenectady International Inc. Microcapsules for the production of storage-stable unsaturated polymer compositions
US20070059526A1 (en) 2002-04-15 2007-03-15 Klaus-Wilhelm Lienert Microcapsules for the production of storage-stable unsaturated polymer compositions
JP2004075914A (en) 2002-08-21 2004-03-11 Toray Ind Inc Epoxy resin composition and prepreg
US7959838B2 (en) 2002-11-28 2011-06-14 Mitsubishi Rayon Co., Ltd. Epoxy resin for prepreg, prepreg, fiber-reinforced composite material and methods for production thereof
US20040242346A1 (en) 2003-05-29 2004-12-02 Keiji Ohama Golf ball and method of manufacturing the same
US20050058822A1 (en) 2003-08-04 2005-03-17 Ittel Steven Dale Fiber-reinforced thermoplastic matrices
JP2005226014A (en) 2004-02-13 2005-08-25 Showa Highpolymer Co Ltd Resin composition for pultrusion, fiber-reinforced resin composition, method for molding the same and molded article
JP4372644B2 (en) 2004-08-25 2009-11-25 カルソニックカンセイ株式会社 Airbag control device
JP4175321B2 (en) 2004-12-01 2008-11-05 株式会社デンソー Pointer instrument
JP5078411B2 (en) 2007-03-31 2012-11-21 財団法人福岡県産業・科学技術振興財団 Integrated circuit module
WO2011073111A1 (en) 2009-12-14 2011-06-23 Gurit (Uk) Ltd Prepregs for manufacturing composite materials
US8715543B2 (en) 2011-03-31 2014-05-06 Ocv Intellectual Capital, Llc Microencapsulated curing agent
US20140200315A1 (en) 2011-03-31 2014-07-17 Ocv Intellectual Capital, Llc Microencapsulated curing agent
JP5138793B2 (en) 2011-06-01 2013-02-06 株式会社サンセイアールアンドディ Game machine

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
Arnaud, et al., "A study of the polymerization of thermosetting polymers, and of a microencapsulated peroxide curing agent", 1998, Travaux Universitaires, Abstract only.
Derwent Abstract, Microcapsules encapuslating oil-soluable organic peroxide, Feb. 21, 1990, JPO, JP 02052038A, p. 1-3.
Koishi, M. "Development and Application of Micro/Nanosystem Capsules and Fine Particles", CMC Publishing, New Materials and Advanced Materials Series, Table of Contents and pp. 94-98, publication page. 2009.
Koishi, M. et al., "Making + Using Microcapsules", Table of Contents, pp. 12-16, publication page, Oct. 18, 2005.
Office action from Japanese Application No. 2014-502836 dated Dec. 14, 2015.
Office action from U.S. Appl. No. 14/213,239 dated Feb. 18, 2016.
Sakurai, Akio, Presentation of Research, Investigation of Microcapsules, pp. 313-317, vol. 60, No. 8, The Japan Reinforced Plastics Society in Aug. 2014.
Summary of Product Features, Lipo Technologies, 9 pgs., available on the world-wide-web before Mar. 31, 2011.

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